JPH0441068B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to optical recording media, particularly heat mode optical recording media. Prior Art Optical recording media have the characteristic that the recording medium does not deteriorate due to wear since the medium and the writing or reading head are not in contact with each other, and for this reason, research and development of various optical recording media are being carried out. Among such optical recording media, heat-mode optical recording media are being actively developed because they do not require image processing in a darkroom. This heat mode optical recording medium is an optical recording medium that uses recording light as heat. One example is a heat mode optical recording medium that uses recording light such as a laser to melt or remove a part of the medium, which is called a pit. There is a pit-forming type in which writing is performed by forming small holes, information is recorded using the pits, and reading is performed by detecting the pits with a readout light. Until now, most of these pit-forming type media, especially those that use a semiconductor laser as a light source, which allows for miniaturization of devices, have recording layers made of materials mainly composed of Te. However, in recent years, it has become clear that Te-based materials are harmful.
In addition, due to the need for higher sensitivity and lower manufacturing costs, Te
In place of conventional recording media, there are an increasing number of proposals and reports on media that use recording layers made of organic materials mainly containing dyes. For example, for He-Ne lasers, squalirium dye [JP-A-56-46221, VBJispson
and CRJones, J.Vac.Sci.Technol., 18 (1)105
(1981)] and metal phthalocyanine dyes (Unexamined Japanese Patent Publication No. 1983)
-82094, 57-82095), etc. There is also an example of using metal phthalocyanine dyes for semiconductor lasers (Japanese Patent Application Laid-Open No. 86795/1986). In both of these, the recording layer is made into a thin film by vapor deposition of dye, and there is no major difference from the Te type in terms of medium production. However, the reflectance of the dye-deposited film to the laser is generally small, and it is not possible to obtain a large S/N ratio with the current conventional method, which obtains the readout signal by changing (reducing) the amount of reflected light due to the pit. . In addition, a transparent substrate carrying a recording layer is used as a medium with a so-called air sandwich structure in which the recording layers are integrated so that they face each other, and writing and reading can be performed through the substrate without reducing the writing sensitivity. However, such a recording/reproducing method is also not possible with a dye-deposited film. This is because a normal transparent resin substrate has a refractive index of a certain value (1.5 for polymethyl methacrylate), a certain degree of surface reflectance (4% for polymethyl methacrylate), and the reflectance of the recording layer through the substrate. This is because, for example, polymethyl methacrylate has a reflectance of about 60% or less, so a recording layer that exhibits only a low reflectance cannot be detected. S/N of readout of recording layer made of dye deposited film
In order to improve the ratio, a vapor-deposited reflective film such as Al is usually interposed between the substrate and the recording layer. In this case, the vapor-deposited reflective film increases the reflectance and increases the S/
This is to improve the N ratio, and by forming pits, the reflective film is exposed and the reflectance increases, or in some cases, the reflective film is removed and the reflectance is decreased. However, recording and playback cannot be performed through the substrate. Similarly, JP-A-55-161690 describes a recording layer consisting of IR-132 dye (manufactured by Kodatsu) and polyvinyl acetate, and JP-A-57-74845 discloses a recording layer consisting of 1,1'-
A recording layer consisting of diethyl-2,2'-tricarbocyanine iodide and nitrocellulose, as well as KYLaw, et al., Appl.Phys.Lett. 39 (9)718
(1981) discloses a medium in which a recording layer made of a dye and a resin is installed by a coating method, such as a recording layer made of 3,3'-diethyl-12-acetylthiatetracarbocyanine and polyvinyl acetate. has been done. However, these cases also have the same drawback as the dye-deposited film in that a reflective film is required between the substrate and the recording layer, and recording and reproduction cannot be performed from the back side of the substrate. In this way, in order to realize a medium with an organic material-based recording layer that allows recording and reproduction through the substrate and is compatible with a medium that has a recording layer made of Te-based material, it is necessary to use an organic material. It is necessary for it to exhibit a large reflectance. However, conventionally, there are very few examples of a single layer of organic material exhibiting high reflectance without laminating a reflective layer. It has been reported that a vapor-deposited film of vanadyl phthalocyanine exhibits slightly high reflectance [P. Kiuits, et al.,
Appl.Phys.Part A 26 (2)101 (1981), Japanese Patent Application Publication No. 1987-
No. 97033], but the writing sensitivity is low, probably due to the high sublimation temperature. In addition, it has been reported that cyanine dyes and merocyanine dyes such as thiazole and quinoline dyes also exhibit high reflectance [Yamamoto et al., Proceedings of the 27th Japan Society of Applied Physics]
1p-P-9 (1980)], and a proposal based on this was made in JP-A-58-112790, but these dyes have low solubility in solvents, especially when installed as a coating film. In addition, it is easily crystallized, and furthermore, it is extremely unstable to read light and immediately bleaches, making it unusable for practical use. In view of these actual circumstances, the present inventors first
He proposed the use of indoline cyanine dyes, which have high solubility in solvents, little crystallization, thermal stability, and high reflectance of paint films, as a single layer film (Japanese Patent Application No. 1983-1999). No. 134397, 57-
No. 134170). In addition, indoline type or thiazole type,
It has been proposed that other cyanine dyes such as quinoline and selenazole dyes can be improved in solubility and prevented from crystallization by introducing long-chain alkyl groups into their molecules. −182589, 57−
177776 etc.). Furthermore, we have proposed adding a quencher to cyanine dyes in order to improve photostability, and in particular to prevent decolorization (reproduction deterioration) caused by readout light (Japanese Patent Application Laid-open No. 166832/1983, 57- 168048 etc.). By the way, as one of the dyes, methine dyes represented by the following general formulas [] and [] are known [JP-A No. 58-65757, No. 57-74845,
Special Publication No. 58-35544, KYLaw and PSVircett
Appl. Phys. Lett. 39 (9) 1718 (1981) etc.]. General formula [] General formula [] {In the above general formulas [] and [], R ₁ represents a substituted or unsubstituted alkyl group, aryl group, aralkyl group, heterocyclic residue, alkoxycarbonyl group, aryloxycarbonyl group, or amino group, or a carboxy group. R ₂ represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, aralkyl group, or heterocyclic residue; R ₃ and R ₄ each represent a substituted or unsubstituted alkyl group, an aryl group, represents an aralkyl group or a heterocyclic residue, Y ₁ and Y ₂ each represent hydrogen, a hydroxy group, a sulfo group, or a substituted or unsubstituted alkyl group, alkoxy group or amino group, L, L ₁ and L ₂ each represents an optionally substituted methine group; m is 1, 2, or 3; } Therefore, it is possible to construct an optical recording medium using such a methine dye, and when forming a recording layer using such a polymethine dye,
It was confirmed that writing and reading can be performed through the substrate even with a single layer film without laminating a reflective layer. However, due to repeated irradiation with readout light during readout after writing, the dye is bleached and the readout S/N ratio deteriorates, resulting in significant reproduction deterioration, which is disadvantageous in that it is not practical. OBJECTS OF THE INVENTION The main object of the present invention is to provide an optical recording medium having a recording layer containing a methine dye, in which reproduction deterioration is improved. These objects are achieved by the invention described below. That is, the present invention provides an optical recording medium having a recording layer made of a dye composition on a substrate, wherein the dye consists of a compound represented by the following general formula [] or [], and the dye composition contains quetia. , an optical recording medium characterized in that the dye is prevented from being degraded by reproduction light. General formula [] General formula [] {In the above general formulas [] and [], R ₁ represents a substituted or unsubstituted alkyl group, aryl group, aralkyl group, heterocyclic residue, alkoxycarbonyl group, aryloxycarbonyl group or amino group, or a carboxy group. R ₂ represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, aralkyl group, or heterocyclic residue; R ₃ and R ₄ each represent a substituted or unsubstituted alkyl group, an aryl group, represents an aralkyl group or a heterocyclic residue, Y ₁ and Y ₂ each represent hydrogen, a hydroxy group, a sulfo group, or a substituted or unsubstituted alkyl group, alkoxy group or amino group, L, L ₁ and L ₂ each represents an optionally substituted methine group; m is 1, 2, or 3; } Specific Configuration of the Invention The specific configuration of the present invention will be described in detail below. The recording layer of the optical recording medium of the present invention contains one of the methine dyes represented by the above general formula [] or [].
Contains more than one species. In the above general formula [], R ₁ is a substituted or unsubstituted alkyl group, preferably having 1 to 18 carbon atoms (which may be chain, cyclic, or chain containing a ring, and is unsubstituted). In addition to these, for example, sulfo groups, carboxy groups, hydroxy groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, cyano groups, halogen atoms, acyl groups, acyloxy groups, vinyl groups, substituted or unsubstituted amino groups, nitro groups, aryl groups having 6 to 10 carbon atoms (for example, phenyl groups, naphthyl groups, in addition to unsubstituted ones, alkyl groups, alkoxy groups, aryloxy group, hydroxy group, sulfo group, carboxy group, halogen, nitro group, substituted or unsubstituted amino group, etc.); Preferably an aralkyl group having 7 to 10 carbon atoms (e.g., benzyl group, phenylethyl group); or phenylpropyl group, in which the aryl moiety may be substituted with the same substituent as in the aryl group); Preferably a hetero group which may have a 5- or 6-membered condensed ring Ring residues (e.g., pyridine-based, thiazole-based, oxazole-based, which may have fused rings,
(Substituted or unsubstituted as above, such as pyridine); Preferably an alkoxy group carbonyl group having 1 to 18 carbon atoms (e.g., methoxycarbonyl group, ethoxycarbonyl group, etc.); Preferably 6 to 11 carbon atoms aryloxycarbonyl group (e.g., phenoxycarbonyl group, unsubstituted or substituted with the same substituent as in the aryl group); or amino group (e.g., dimethylamino group, diethylamino group, etc.) ): And it is a carboxy group. R ₂ , R ₃ and R ₄ may be the same or different, but each is a substituted or unsubstituted alkyl group, preferably having 1 to 18 carbon atoms (whether chain or cyclic, containing a ring). It may be chain-like, and in addition to unsubstituted ones, for example, sulfo group, carboxy group, hydroxy group, alkoxy group, aryloxy group, alkoxycarbonyl group, cyano group, halogen atom, acyl group, acyloxy group, vinyl group, substituted or unsubstituted amino group, nitro group, alkylthio group, etc.); preferably an aryl group having 6 to 10 carbon atoms (for example, phenyl group, naphthyl group, and unsubstituted (in addition to those substituted with an alkyl group, an alkoxy group, an aryloxy group, a hydroxy group, a sulfo group, a carboxy group, a halogen, a nitro group, a substituted or unsubstituted amino group); preferably 7 to 10 carbon atoms. an aralkyl group (for example, a benzyl group, phenylethyl group, phenylpropyl group, etc., in which the aryl moiety may be substituted with the same substituent as in the aryl group); preferably 5- or 6-membered Heterocyclic residues that may have a condensed ring (e.g., pyridine, thiazole, oxazole,
(Substituted or unsubstituted products similar to those mentioned above, such as pyridine series). In this case, R ₂ may be hydrogen. Furthermore, Y ₁ and Y ₂ in the general formula [] are
They may be the same or different from each other, but each is substituted or unsubstituted, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.); preferably a carbon atom Alkoxy groups of numbers 1 to 4 (e.g., methoxy group, ethoxy group, propoxy group, butoxy group, etc.); or Amino groups (e.g., dimethylamino group, diethylamino group, acetamido group, propionamide group, benzamide group, etc.): or , hydrogen atom, hydroxy group, and sulfo group. And, any one of L, L ₁ and L ₂ represents a methine group which may be substituted with a methyl group, a phenyl group, a halogen atom or the like. Furthermore, m is 1, 2 or 3. Specific examples of these methine dyes are listed below.

【table】

【table】

【table】

【table】

【table】

[Table] These dyes are synthesized according to known methods. Further, such a dye is usually contained in the recording layer in the form of a monomer, but may be contained in the form of a polymer if necessary. In this case, the polymer has two or more molecules of a dye, and may be a condensate of these dyes. For example, single or co-condensates of the above dyes having one or more functional groups such as -OH, -COOH, -SO ₃ H, etc., or with these, dialcohols, dicarboxylic acids, or their salts. There are cocondensation components such as diamines, di- and triisocyanates, diepoxy compounds, acid anhydrides, dihydrazides, and diiminocarbonates, and cocondensation products with other pigments. Alternatively, the dye having the above functional group may be crosslinked with a metal crosslinking agent alone or together with a spacer component or other dye. In this case, the metal crosslinking agents include alkoxides of titanium, zircon, aluminum, etc., chelates of titanium, zircon, aluminum, etc. (e.g., β-diketones, ketoesters, hydroxycarboxylic acids and their esters, ketoalcohols, aminoalcohols, enols) acylates of titanium, zircon, aluminum, etc.). Furthermore, -OH group, -OCOR group and -COOR
One or more types of dyes having at least one group (wherein R is a substituted or unsubstituted alkyl group or aryl group), or these together with other spacer components or other dyes It is also possible to use a compound in which the compound is bonded with a -COO- group by a transesterification reaction. In this case, the transesterification reaction is preferably carried out using an alkoxide such as titanium, zircon, or aluminum as a catalyst. Additionally, the dyes described above may be bound to a resin. In such a case, a resin having a predetermined group is used, and the side chain of the resin is subjected to a condensation reaction, transesterification reaction, or crosslinking, as in the case of the polymer described above. The dyes are linked via a spacer component, etc., if necessary. Such dyes may be used in combination with other dyes to form the recording layer as long as the effects of the present invention are not impaired. The recording layer may contain a resin if necessary. The resin used is preferably a self-oxidizing, depolymerizable or thermoplastic resin. Among these, resins that can be particularly suitably used include the following. () Polyolefin polyethylene, polypropylene, poly4-methylpentene-1, etc. () Polyolefin copolymer For example, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer,
Ethylene-maleic anhydride copolymer, ethylene propylene terpolymer (EPT), etc. In this case, the polymerization ratio of the comonomers can be arbitrary. () Vinyl chloride copolymer For example, vinyl acetate-vinyl chloride copolymer,
Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-maleic anhydride copolymer, copolymer of acrylic acid ester or methacrylic acid ester and vinyl chloride, acrylonitrile-vinyl chloride copolymer, vinyl chloride ether copolymer,
Ethylene or propylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer with vinyl chloride graft polymerized, etc. In this case, the copolymerization ratio can be arbitrary. () Vinylidene chloride copolymer Vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-vinyl chloride-acrylonitrile copolymer, vinylidene chloride-butadiene-vinyl halide copolymer, etc. In this case, the copolymerization ratio can be arbitrary. () Polystyrene () Styrene copolymer For example, styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile-
Butadiene copolymer (ABS resin), styrene-
Maleic anhydride copolymer (SMA resin), styrene-acrylic acid ester-acrylamide copolymer, styrene-butadiene copolymer (SBR), styrene-vinylidene chloride copolymer,
Styrene-methyl methacrylate copolymer, etc. In this case, the copolymerization ratio can be arbitrary. () Styrene type polymers For example, α-methylstyrene, p-methylstyrene, 2,5-dichlorostyrene, α,β-
Vinylnaphthalene, α-vinylpyridine, acenaphthene, vinylanthracene, etc., or copolymers thereof, such as copolymers of α-methylstyrene and methacrylic acid ester. () Coumarone-indene resin A copolymer of coumaron-indene-styrene. () Terpene resin or picolite For example, terpene resin which is a polymer of limonene obtained from α-pinene, or picolite obtained from β-pinene. () Acrylic resin Particularly preferred is one containing an atomic group represented by the following formula. formula In the above formula, R ₁₀ represents a hydrogen atom or an alkyl group, and R ₂₀ represents a substituted or unsubstituted alkyl group. In this case, in the above formula, R ₁₀ is a hydrogen atom or a carbon atom number of 1 to 1.
4 is preferably a lower alkyl group, particularly a hydrogen atom or a methyl group. Further, R ₂₀ may be a substituted or unsubstituted alkyl group, but the alkyl group preferably has 1 to 8 carbon atoms, and when R ₂₀ is a substituted alkyl group, the alkyl group preferably has 1 to 8 carbon atoms. The substituent for the group is preferably a hydroxyl group, a halogen atom, or an amino group (particularly a dialkylamino group). The atomic group represented by the above formula may form a copolymer with other repeating atomic groups to constitute various acrylic resins, but usually one type of atomic group represented by the above formula is used. Alternatively, an acrylic resin is formed by forming a homopolymer or copolymer having two or more repeating units. (xi) Polyacrylonitrile (xii) Acrylonitrile copolymer For example, acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-vinylpyridine copolymer polymer, acrylonitrile-methyl methacrylate copolymer, acrylonitrile-butadiene copolymer,
Acrylonitrile-butyl acrylate copolymer, etc. In this case, the copolymerization ratio can be arbitrary. () Diacetone acrylamide polymer Diacetone acrylamide polymer made by reacting acetone with acrylonitrile. () Polyvinyl acetate () Vinyl acetate copolymer For example, a copolymer with acrylic acid ester, vinyl ether, ethylene, vinyl chloride, etc. The copolymerization ratio may be arbitrary. () Polyvinyl ether For example, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl butyl ether, etc. () Polyamide In this case, polyamides include nylon 6, nylon 6-6, nylon 6-10, nylon 6-12, nylon 9, nylon 11, nylon
In addition to regular homonylon such as 12 and nylon 13,
Nylon 6/6-6/6-10, Nylon 6/6
-6/12, nylon 6/6-6/11, or modified nylon in some cases. () Polyester For example, oxalic acid, succinic acid, maleic acid,
Various dibasic acids such as aliphatic dibasic acids such as adipic acid and sebastenic acid, or aromatic dibasic acids such as isophthalic acid and terephthalic acid, ethylene glycol, tetramethylene glycol,
Condensates and copolymers with glycols such as hexamethylene glycol are suitable. Among these, condensates of aliphatic dibasic acids and glycols and cocondensates of glycols and aliphatic dibasic acids are particularly suitable. Furthermore, for example, glyptal resin, which is a condensate of phthalic anhydride and glycerin, can be used as a fatty acid,
Modified glyptal resins that are esterified with natural resins and the like are also preferably used. () Polyvinyl acetal resin Both polyvinyl formal and polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol are preferably used. In this case, the degree of acetalization of the polyvinyl acetal resin can be arbitrary. () Polyurethane resin Thermoplastic polyurethane resin with urethane bonds. Particularly suitable are polyurethane resins obtained by condensation of glycols and diisocyanates, particularly polyurethane resins obtained by condensation of alkylene glycol and alkylene diisocyanate. () Polyether Styrene-formalin resin, ring-opening polymer of cyclic acetal, polyethylene oxide and glycol, polypropylene oxide and glycol, propylene oxide-ethylene oxide copolymer, polyphenylene oxide, etc. () Cellulose derivatives such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose,
Various esters and ethers of cellulose, such as ethylhydroxyethylcellulose, and mixtures thereof. () Polycarbonate For example, various polycarbonates such as polydioxydiphenylmethane carbonate and dioxydiphenylpropane carbonate. () Ionomer Na, Li, methacrylic acid, acrylic acid, etc.
Zn, Mg salt, etc. () Ketone resin For example, a condensate of a cyclic ketone such as cyclohexanone or acetophenone and formaldehyde. () Xylene resin For example, a condensate of m-xylene or mesitylene and formalin, or a modified product thereof. () Petroleum resins _C5 type, _C9 type, _C5 - _C9 copolymer type, dicyclopentadiene type, or copolymers or modified products thereof. () A blend of two or more of the above () to (), or a blend with other thermoplastic resins. Note that the molecular weight of the self-oxidizing resin, thermoplastic resin, etc. may vary. Such a resin and the above-mentioned dye are usually formed in a wide range of weight ratio of 1:0.1 to 100. A quencher is contained in such a recording layer. This reduces reproduction deterioration of the S/N ratio due to repeated irradiation with readout light. In addition, light resistance is improved by storage in a bright room. Various quenchers can be used, but in particular, the quencher reduces regeneration deterioration,
A transition metal chelate compound is preferred because it has good compatibility with the dye-binding resin. In this case, the central metals are Ni,
Co, Cu, Mn, Pd, Pt, etc. are preferred, and the following compounds are particularly preferred. (1) Acetylacetonate chelate system Q1-1 Ni () acetylacetate Q1-2 Cu () acetylacetate Q1-3 Mn () acetylacetate Q1-4 Co () acetylacetate (2) In the following formula The bisdithio-α-diketone system shown Here, R ⁽¹⁾ to ^{R (4)} represent a substituted or unsubstituted alkyl group or aryl group, and M is
Represents transition metal atoms such as Ni, Co, Cu, Pd, and Pt. In this case, M has a negative charge and may form a salt with a cation (Cat) such as a quaternary ammonium ion. In addition, in the following description, ph is a phenyl group, ψ is a 1,4-phenylene group, and ψ' is a 1,2-
The phenylene group, benz, represents that adjacent groups on the ring bond to each other to form a fused benzene ring.

[Table] (3) Bisphenyldithiol system represented by the following formula Here, R ⁽⁵⁾ and R ⁽⁶⁾ represent hydrogen, an alkyl group such as a methyl group or an ethyl group, a halogen atom such as Cl, or an amino group such as a dimethylamino group or a diethylamino group, and M is , represents transition metal atoms such as Ni, Co, Cu, Pd, and Pt. In addition, M in the above structure has a negative charge and may form a salt with a cation (Cat) such as a quaternary ammonium ion, and furthermore, other ligands may be bonded above and below M. It's okay. Examples of this include the following:

【table】

[Table] In addition, those described in JP-A-50-45027 and the patent application dated September 5, 1982. (4) Dithiocarbamate chelate system represented by the following formula Here, R ⁽⁹⁾ and R ⁽¹⁰⁾ represent an alkyl group. Further, M represents a transition metal atom such as Ni, Co, Cu, Pd, or Pt. Q4-1R ⁽⁹⁾ , R ⁽¹⁰⁾ /C ₄ H ₉ M/Ni (5) Compound represented by the following formula Here, M represents a transition metal atom, and Q ¹
teeth,

[expression] or

【formula】 and Cat represents a cation.

[Table] Other items described in Japanese Patent Application No. 58-125654. (6) Compound represented by the following formula Here, M represents a transition metal atom, A is S,

[expression] or

[Formula] represents R ⁽¹¹⁾ and R ⁽¹²⁾ , respectively, CN,
COR ⁽¹³⁾ , COOR ⁽¹⁴⁾ , CONR ⁽¹⁵⁾ R ⁽¹⁶⁾ or
represents SO ₂ R ⁽¹⁷⁾ , R ⁽¹³⁾ to ^{R (17)} each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group, and Q ² forms a 5- or 6-membered ring. Cat represents a cation, and n is 1 or 2.

【table】

【table】 \


CN


In addition, those described in Japanese Patent Application No. 58-127074. (7) Compound represented by the following formula Here, M represents a transition metal atom, Cat represents a cation, and n is 1 or 2. M Cat Q7-1 Ni 2 [(n-C ₄ H ₉ ) ₃ H Q7-2 Ni 2 [n-C ₁₆ H ₃₃ (CH ₃ ) ₃ N] In addition, the thing. (8) Bisphenylthiol system Q8-1 Ni-bis(octylphenyl)sulfide (9) Thiocatechol chelate system represented by the following formula Here, M represents a transition metal atom such as Ni, Co, Cu, Pd, or Pt. In addition, M has a single charge and is a cation (Cat).
and the benzene ring may have a substituent. M Cat Q9−1 Ni N ⁺ (C ₄ H ₉ ) ₄ (10) Compound represented by the following formula Here, R ⁽¹⁸⁾ represents a monovalent group, l is 0 to 6, M represents a transition metal atom, and Cat represents a cation.

[Table] Other items described in Japanese Patent Application No. 143531/1982. (11) Compounds represented by both formulas below Here, in the above general formulas [] and [], R ⁽²⁰⁾ , R ⁽²¹⁾ , R ⁽²²⁾ and R ⁽²³⁾ each represent a hydrogen atom or a monovalent group, and R ⁽²⁴⁾ , R ⁽²⁵⁾ , R ⁽²⁶⁾ and R ⁽²⁷⁾ represent a hydrogen atom or a monovalent group, but R ⁽²⁴⁾ , R ⁽²⁵⁾ and R ⁽²⁵⁾
R ⁽²⁶⁾ , R ⁽²⁶⁾ and R ⁽²⁷⁾ may be combined with each other to form a 6-membered ring. Moreover, M represents a transition metal atom.

[Table] Other items described in Japanese Patent Application No. 145294/1982. (12) Compound represented by the following formula Here, M represents Pt, Ni or Pd,
X ₁ , X ₂ , X ₃ and X ₄ each represent O or S. M X ₁ X _{2 X 3} (13) Compound represented by the following formula Here, R ⁽³¹⁾ is a substituted or unsubstituted alkyl group or aryl group, and R ⁽³²⁾ , R ⁽³³⁾ , R ⁽³⁴⁾ and R ⁽³⁵⁾ are hydrogen atoms or monovalent groups. , but R ⁽³²⁾ and R ⁽³³⁾ , R ⁽³³⁾ and
R ⁽³⁴⁾ , R ⁽³⁴⁾ and R ⁽³⁵⁾ may be combined with each other to form a 6-membered ring. Moreover, M represents a transition metal atom.

[Table] Other items described in Japanese Patent Application No. 151928/1982. (14) Compounds represented by both formulas below Here, R ⁽⁴¹⁾ , R ⁽⁴²⁾ , R ⁽⁴³⁾ and R ⁽⁴⁴⁾ each represent a hydrogen atom or a monovalent group,
R ⁽⁴¹⁾ and R ⁽⁴²⁾ , R ⁽⁴²⁾ and R ⁽⁴³⁾ , and R ⁽⁴³⁾ and R ⁽⁴⁴⁾ may be combined with each other to form a 6-membered ring. Furthermore, R ⁽⁴⁵⁾ and R ⁽⁴⁶⁾ are hydrogen atoms or 1
Represents a valence group. Furthermore, M represents a transition metal atom.

[Table] Other items described in Japanese Patent Application No. 151929/1982. (15) Compound represented by the following formula Here, R ⁽⁵¹⁾ , R ⁽⁵²⁾ , R ⁽⁵³⁾ , R ⁽⁵⁴⁾ , R ⁽⁵⁵⁾ ,
R ⁽⁵⁶⁾ , R ⁽⁵⁷⁾ and R ⁽⁵⁸⁾ each represent a hydrogen atom or a monovalent group, but R ⁽⁵¹⁾ and R ⁽⁵²⁾ , R ⁽⁵²⁾ and R ⁽⁵³⁾ , R ⁽⁵³⁾ and R ⁽⁵⁴⁾ , R ⁽⁵⁵⁾
and R ⁽⁵⁶⁾ , R ⁽⁵⁶⁾ and R ⁽⁵⁷⁾ , and R ⁽⁵⁷⁾ and R ⁽⁵⁸⁾ may be bonded to each other to form a 6-membered ring. R ⁽⁵⁹⁾ represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. X represents halogen. M represents a transition metal atom.

[Table] Other items described in Japanese Patent Application No. 153392/1982. (16) Salicylaldehyde oxime system represented by the following formula Here, R ⁽⁶⁰⁾ and R ⁽⁶¹⁾ represent an alkyl group, and M represents a transition metal atom such as Ni, Co, Cu, Pd, Pt, etc.

[Table] (17) Thiobisphenolate chelate system represented by the formula below Here, M is the same as above, R ⁽⁶⁵⁾ and
R ⁽⁶⁶⁾ represents an alkyl group. Further, M has a negative charge and may form a salt with a cation (Cat).

[Table] ⁺
Q17−2 t−C ₈ H ₁₇ Co NH ₃ (C ₄ H ₉ )
Q17−3 t−C ₈ H ₁₇ Ni −
(18) Phosphonous acid chelate system represented by the following formula Here, M is the same as above, R ⁽⁷¹⁾ and
R ⁽⁷²⁾ represents a substituent such as an alkyl group or a hydroxyl group. R ⁽⁷¹⁾ , R ⁽⁷²⁾ M Q18-1 3-t-C ₄ H ₉ , 5-t-C ₄ H ₉ , 6-OH N
i (19) Compounds represented by the following formulas Here, R ⁽⁸¹⁾ , R ⁽⁸²⁾ , R ⁽⁸³⁾ and R ⁽⁸⁴⁾ represent a hydrogen atom or a monovalent group, but R ⁽⁸¹⁾ , R ⁽⁸²⁾ and R ⁽⁸²⁾ R ⁽⁸³⁾ , R ⁽⁸³⁾ and R ⁽⁸⁴⁾ may be bonded to each other to form a 6-membered ring. R ⁽⁸⁵⁾ and R ⁽⁸⁸⁾ each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. R ⁽⁸⁶⁾ represents a hydrogen atom, a hydrogen group, or a substituted or unsubstituted alkyl group or aryl group. R ⁽⁸⁷⁾ represents a substituted or unsubstituted alkyl group or aryl group. Z represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring. M represents a transition metal atom.

[Table] Other items described in Japanese Patent Application No. 153393/1982. (20) Compound represented by the following formula Here, R ⁽⁹¹⁾ and R ⁽⁹²⁾ are each a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an acyl group, an N-alkylcarbamoyl group,
It represents an N-arylcarbamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and M represents a transition metal atom.

[Table] Other items described in Japanese Patent Application No. 58-155359. In addition, other quenchers include the following. (21) Benzoate Q21-1 Existing chemical substance 3-3040 [Tinuvin-
120 (manufactured by Ciba Geigy)] (22) Hindered amine Q22-1 Existing chemical substance 5-3732 [SANOL LS
-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)] Each of these quenchers has a
It is contained in an amount of about 0.01 to 12 mol, particularly about 0.1 to 1.2 mol. Note that the maximum absorption wavelength of the quencher is preferably greater than or equal to the maximum absorption wavelength of the dye used. As a result, reproduction deterioration becomes extremely small. In this case, the difference between the two is preferably 0 or 350 nm or less. In order to form such a recording layer, it is generally necessary to apply it by coating according to a conventional method. The thickness of the recording layer is usually 0.03 to 10 μm.
It is considered to be a degree. In addition, such a recording layer may contain other dyes, other polymers or oligomers, various plasticizers, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, and antioxidants. , a crosslinking agent, etc. may be contained. In order to form such a recording layer, it is usually enough to coat the substrate with a predetermined solvent and dry it. Examples of solvents used for coating include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, esters such as butyl acetate, ethyl acetate, carbitol acetate, and butyl carbitol acetate, and ethers such as methyl cellosolve and ethyl cellosolve. , aromatic systems such as toluene and xylene, halogenated alkyl systems such as dichloroethane, and alcohol systems. There is no particular restriction on the material of the substrate on which such a recording layer is provided, and it may be made of any of various resins, glass, ceramics, metals, etc., but it must be substantially transparent to writing light and reading light. Preferably. Further, its shape may be a tape, a drum, a belt, etc. depending on the intended use. Note that the base body usually has a tracking groove. In addition, resin materials for the base include polymethyl methacrylate, acrylic resin, epoxy resin,
Non-grooved substrates such as polycarbonate resins, polysulfone resins, polyethersulfones, methylpentene polymers, etc. are suitable. These substrates can also be coated with a primer to improve solvent resistance, wettability, surface tension, thermal conductivity, etc. As the primer, for example, titanium-based, silane-based, or aluminum-based coupling agents, various photosensitive resins, and the like can be used. Further, various uppermost protective layers, half mirror layers, etc. can be provided on the recording layer, if necessary. However, it is preferable that the recording layer is a single layer film and that a reflective layer is not laminated above or below the recording layer. The medium of the present invention may have the above-mentioned recording layer on one surface of such a substrate, or may have recording layers on both surfaces thereof. Also,
Two substrates with recording layers coated on one side are used, with the recording layers facing each other. It is also possible to make them face each other with a predetermined gap and seal them to prevent dust and scratches from forming. Specific effects of the invention When the medium of the invention is running or rotating,
Recording light is irradiated in a pulsed manner. At this time, due to the heat generated by the dye in the recording layer, the dye melts and pits are formed. The pits thus formed are read out by detecting the reflected or transmitted light of the readout light, particularly the reflected light, while the medium is running or rotating. In this case, recording and reading may be performed from the substrate side or from the recording layer side, but it is preferable to perform the recording and reading through the substrate. It is also possible to erase the pits once formed in the recording layer with light or heat and rewrite. Note that the recording or reading light can be a semiconductor laser, He-Ne laser, Ar laser, He
-Cd laser etc. can be used. Specific Effects of the Invention According to the present invention, reproduction deterioration caused by read light is extremely reduced. In addition, the light resistance has been significantly improved, and there is extremely little deterioration in characteristics due to storage in a bright room. Further, there is little deterioration in characteristics even when erasing and rewriting are performed. Furthermore, writing and reading can be performed through the substrate without laminating a reflective layer. It also has good solubility and little crystallization. Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in further detail. Example 1 Dye D, Resin R, and Quencher Q shown in Table 1 below were dissolved in a predetermined solvent in the proportions shown in Table 1, and deposited on an acrylic disk substrate with a diameter of 30 cm and a thickness of 0.07 μm. A variety of media were obtained by coating and layering. In this case, in Table 1, NC is the nitrogen content
It is nitrocellulose with a viscosity of 11.5-12.2% and 80 seconds based on JIS K 6703. Furthermore, the dyes used were those of the numbers exemplified above. In addition, the quencher used is indicated by the number exemplified above. Table 1 shows the R/D weight ratio and Q/D
The weight ratio of For each medium thus created, 1 mW
He−Ne laser readout light, 1μsec width, 3K
After 5 minutes of irradiation as a Hz pulse in a static state, the change in reflectance (%) from the back side of the substrate was measured.

[Table] From the results shown in Table 1, the effects of the present invention are clear. Example 2 Using media Nos. 2 to 7 of Example 1, writing was performed in the same manner as in Example 1, and then erasing was performed by heating the media at 150°C for 15 seconds using an infrared heater. With the medium, repeated erasing,
It was confirmed that rewriting could be performed successfully.

Claims (1)

[Claims] 1. An optical recording medium having a recording layer made of a dye composition on a substrate, wherein the dye consists of a compound represented by the following general formula [] or [], and a quencher is included in the dye composition. An optical recording medium characterized in that the dye is contained therein to prevent deterioration of the dye due to reproduction light. General formula [] General formula [] {In the above general formulas [] and [], R ₁ represents a substituted or unsubstituted alkyl group, aryl group, aralkyl group, heterocyclic residue, alkoxycarbonyl group, aryloxycarbonyl group, or amino group, or a carboxy group. R ₂ represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, aralkyl group, or heterocyclic residue; R ₃ and R ₄ each represent a substituted or unsubstituted alkyl group, an aryl group, represents an aralkyl group or a heterocyclic residue, Y ₁ and Y ₂ each represent hydrogen, a hydroxy group, a sulfo group, or a substituted or unsubstituted alkyl group, alkoxy group or amino group, L, L ₁ and L ₂ each represents an optionally substituted methine group; m is 1, 2, or 3; } 2. The optical recording medium according to claim 1, wherein a resin is contained in the dye composition. 3. The optical recording medium according to claim 1 or 2, wherein the quencher is a transition metal chelate compound. 4. The optical recording medium according to any one of claims 1 to 3, in which a reflective layer is not laminated on the recording layer. 5. The optical recording medium according to any one of claims 1 to 4, in which writing and reading are performed through the substrate.